Fluoroacrylate-multifunctional acrylate copolymer compositions

ABSTRACT

A composition comprises a copolymer comprising repeating units derived from at least one co-reactant comprising two or more acrylate groups and repeating units derived from a fluoroacrylate comprising the reaction product of: (a) at least one fluorochemical alcohol represented by the formula: 
 
C 4 F 9 —X—OH 
 
wherein:  
                 
R=hydrogen or an alkyl group of 1 to 4 carbon atoms, m=2 to 8, 
             R f =C n F 2n+1 , n=1 to 5, y 32 0 to 6, and q=1 to 8; (b) at least one unbranched symmetric diisocyanate; and (c) at least one hydroxy-terminated alkyl (meth)acrylate or 2-fluoroacrylate monomer having 2 to about 30 carbon atoms in its alkylene portion; wherein the composition is coatable.

FIELD

This invention relates to compositions comprisingfluoroacrylate-multifunctional acrylate copolymers, and to a method formaking the compositions.

BACKGROUND

Pressure sensitive adhesives (PSAs) are adhesives that adhere tosubstrates merely with the application of light pressure (for example,finger pressure). Silicone-based PSA systems are sometimes preferred forapplications requiring high temperature and/or humidity resistance.

Because PSAs adhere to substrates so easily, they are typically providedon a release liner (for example, a backing coated with release coating)to protect them before use. Fluorinated release coatings are often usedto provide release properties to silicone-based PSAs because of theirlow surface energy. Many fluorinated release coatings are not suitable,however, for solvent casting of silicone-based PSAs because they havesignificant solubility in common solvents.

SUMMARY

In view of the foregoing, we recognize that there is a need in the artfor release coatings that are suitable for silicone-based PSA releaseliners, but that have improved solvent resistance.

Briefly, in one aspect, the present invention provides coatablecompositions that are useful as release coatings for PSAs such as, forexample, silicone-based PSAs. The compositions comprise a copolymercomprising repeating units derived from at least one co-reactantcomprising two or more acrylate groups and repeating units derived froma fluoroacrylate comprising the reaction product of:

-   -   (a) at least one fluorochemical alcohol represented by the        formula:        C₄F₉—X—OH    -   wherein:        -   R=hydrogen or an alkyl group of 1 to 4 carbon atoms,        -   m=2 to 8,        -   R_(f)=C_(n)F_(2n+1),        -   n=1 to 5,        -   y=0 to 6, and        -   q=1 to 8;    -   (b) at least one unbranched symmetric diisocyanate; and    -   (c) at least one hydroxy-terminated alkyl (meth)acrylate or        2-fluoroacrylate monomer having 2 to about 30 carbon atoms in        its alkylene portion.

As used herein, the term “(meth)acrylate” refers to both acrylates andmethacrylates; and the term “coatable” or “coatable composition” meansthat the composition is soluble or dispersible in solvents or water andis substantially gel-free and, that it can be applied to a substrateusing standard coating methods, and that it forms a film upon heating orcuring. Gels are single macromolecules formed as an infinite network bycrosslinking of polymer chains, and are thus insoluble in all solventsbelow their decomposition temperature (see, for example, Principles ofPolymerization, 3^(rd) ed., Wiley & Sons, p. 108, (1991)).

The present invention also provides coatable compositions comprising acopolymer comprising the reaction product of

(a) a fluoroacrylate represented by the following general formula:C₄F₉—X—OC(O)NH-A-HNC(O)O—(C_(p)H_(2p))(O)COC(R′)═CH₂

wherein:

-   -   R=H or an alkyl group of 1 to 4 carbon atoms,    -   m=2 to 8,    -   R_(f)=C_(n)F_(2n+1),    -   n=1 to 5,    -   y=0 to 6,    -   q=1 to 8,    -   A=an unbranched symmetric alkylene group, arylene group, or        aralkylene group,    -   p=2 to 30, and    -   R′=H, CH₃, or F; and

(b) at least one co-reactant comprising two or more acrylate groups.

Multifunctional acrylates (that is, compounds comprising two or moreacrylate groups) are known crosslinkers and are generally avoided duringthe production of linear polyacrylates in order to avoid forminginsoluble or gel-containing product. Gel can interfere with themechanical delivery of a coating (for example, by plugging the orifices)and with film-formation (see, for example, Organic Coatings, Science andTechnology, vol. 1, Wicks et al., Wiley & Sons, p. 38 (1992)).Surprisingly, however, the fluoroacrylate-multifunctional acrylatecompositions of the present invention are coatable.

The coatable compositions of the invention are useful as release coatingfor PSAs, including silicone-based PSAs. Release coatings comprising thecompositions of the invention have low peel force (for example, about 5to about 400 g/cm; preferably, about 10 to about 200 g/cm) and highreadhesion (for example, not more than about 5% adhesion loss after anadhesive is in contact with the release coating), even after ageing. Thecured release coatings also have relatively low solubility in commonsolvents, and can therefore be used with solvent casted PSAs.

The compositions of the invention therefore meet the need in the art forrelease coating compositions that are useful as release coatings forPSAs such as, for example, silicone-based PSAs.

In addition, the compositions of the invention exhibit good water- andoil-repellency properties. In light of the prior art, one would expectthat compositions comprising fluoroacrylates derived from shorterperfluorinated chains would not be as effective at imparting water- andoil-repellency as those derived from longer perfluorinated chains suchas, for example, 8 carbon atom chains (see, for example, U.S. Pat. Nos.2,803,615 (Ahlbrecht et al.) and U.S. Pat. No. 3,787,351 (Olson)). Thecompositions of the invention comprise fluoroacrylates that haveperfluorinated groups of 4 carbon atoms, yet surprisingly they exhibitwater- and oil-repellency comparably to compositions comprisingfluoroacrylates derived from longer perfluorinated chains. This isparticularly advantageous because fluoroacrylates that have short chainperfluorinated groups are believed to be less toxic and lessbioaccumulative than longer chain perfluorinated groups (see, forexample, WO 01/30873).

In another aspect, this invention also provides a method of makingcoatable compositions comprising reacting a fluoroacrylate with at leastone co-reactant comprising two or more acrylate groups, and optionallyat least one chain transfer agent, in a reaction solvent to form acopolymer; wherein the fluoroacrylate, co-reactant, and chain transferagent are present in an amount up to about 35 weight percent(preferably, between about 5 and about 25 weight percent), the weightpercent being based upon the total weight of the monomers and thesolvent; and the fluoroacrylate is represented by the following generalformula:C₄F₉—X—OC(O)NH-A-HNC(O)O—(C_(p)H_(2p))(O)COC(R′)═CH₂

wherein:

-   -   R=H or an alkyl group of 1 to 4 carbon atoms,    -   m=2 to 8,    -   R_(f)=C_(n)F_(2n+1),    -   n=1 to 5,    -   y=0 to 6,    -   q=1 to 8,    -   A=an unbranched symmetric alkylene group, arylene group, or        aralkylene group,    -   p=2 to 30, and    -   R′=H, CH₃, or F.

DETAILED DESCRIPTION

Fluoroacrylates useful in the invention are the reaction product of afluorochemical alcohol, at least one unbranched symmetric diisocyanate,and at least one hydroxy-terminated alkyl (meth)acrylate or2-fluoroacrylate monomer.

Useful fluorochemical alcohols can be represented by the formula:C₄F₉—X—OH

wherein:

-   -   R=hydrogen or an alkyl group of 1 to 4 carbon atoms,    -   m=2 to 8,    -   R_(f)=C_(n)F_(2n+1),    -   n=1 to 5,    -   y=0 to 6, and    -   q=1 to 8.

Representative examples of suitable alcohols include C₄F₉SO₂NH(CH₂)₂OH,C₄F₉SO₂NCH₃(CH₂)₂OH, C₄F₉SO₂NCH₃(CH₂)₄OH, C₄F₉SO₂NC₂H₅(CH₂)₆OH,C₄F₉(CH₂)₄OH, C₄F₉CONH(CH₂)₄OH, C₄F₉SO₂NCH₃(CH₂)₃OH, C₄F₉SO₂NH(CH₂)₆OH,C₄F₉CH₂OH, C₄F₉CONH(CH₂)₈OH, C₄F₉(CH₂)₂OH, C₄F₉SO₂NCH₃(CH₂)₂OH,C₄F₉CONH(CH₂)₂OH, C₄F₉SO₂NCH₃(CH₂)₆OH, C₄F₉SO₂NH(CH₂)₇OH,C₄F₉SO₂NC₃H₇(CH₂)₂OH, C₄F₉SO₂NC₄H₉(CH₂)₂OH, C₄F₉CONH(CH₂)₂OH, andC₄F₉(CH₂)₄OH.

Preferably, m is 2 to 4. Preferably, q is 2.

Preferably, X is

More preferably, X is

Most preferably, X is selected from the group consisting of

Preferred fluorochemical alcohols include, for example,C₄F₉SO₂NCH₃(CH₂)₂OH, C₄F₉SO₂NCH₃(CH₂)₄OH, and C₄F₉(CH₂)₂OH. A morepreferred fluorochemical alcohol is C₄F₉SO₂NCH₃(CH₂)₂OH.

Symmetric diisocyanates are diisocyanates that meet the three elementsof symmetry as defined by Hawley's Condensed Chemical Dictionary 1067(1997). First, they have a center of symmetry, around which theconstituent atoms are located in an ordered arrangement. There is onlyone such center in the molecule, which may or may not be an atom.Second, they have a plane of symmetry, which divides the molecule intomirror-image segments. Third, they have axes of symmetry, which can berepresented by lines passing through the center of symmetry. If themolecule is rotated, it will have the same position in space more thanonce in a complete 360° turn.

As used herein, the term “unbranched” means that the symmetricdiisocyanate does not contain any subordinate chains of one or morecarbon atoms.

Representative examples of unbranched symmetric diisocyanates include4,4′-diphenylmethane diisocyanate (MDI), 1,6-hexamethylene diisocyanate(HDI), 1,4-phenylene diisocyanate (PDI), 1,4-butane diisocyanate (BDI),1,8-octane diisocyanate (ODI), 1,12-dodecane diisocyanate, and1,4-xylylene diisocyanate (XDI). Preferably, unbranched symmetricdiisocyanates are aromatic.

Preferred unbranched symmetric diisocyanates include, for example, MDI,HDI, and PDI. A more preferred unbranched symmetric diisocyanate is MDI.In its pure form, MDI is commercially available as Isonate™ 125M fromDow Chemical Company (Midland, Mich.), and as Mondur™ from BayerPolymers (Pittsburgh, Pa.).

Hydroxy-terminated alkyl (meth)acrylate and 2-fluoroacrylate monomersthat are useful in the fluoroacrylates of the invention can have from 2to about 30 carbon atoms (preferably, from 2 to about 12 carbon atoms)in their alkylene portion.

Preferably, the hydroxy-terminated alkyl(meth)acrylate monomer is ahydroxy-terminated alkyl acrylate. Preferred hydroxy-terminated alkylacrylates include, for example, hydroxy ethyl acrylate, hydroxy butylacrylate, hydroxy hexyl acrylate, hydroxy decyl acrylate, hydroxydodecyl acrylate, and mixtures thereof.

The fluoroacrylates useful in the invention can be prepared, forexample, by first combining the fluorochemical alcohol and unbranchedsymmetric diisocyanate in a solvent, and then adding thehydroxy-terminated alkyl(meth)acrylate. Useful solvents include esters(for example, ethyl acetate), ketones (for example, methyl ethylketone), ethers (for example, methyl-tert-butyl ether), and aromaticsolvents (for example, toluene).

Preferably, the reaction mixture is agitated. The reaction can generallybe carried out at a temperature between room temperature and about 120°C. (preferably, between about 50° C. and about 70° C.).

Typically the reaction is carried out in the presence of a catalyst.Useful catalysts include bases (for example, tertiary amines, alkoxides,and carboxylates), metal salts and chelates, organometallic compounds,acids and urethanes. Preferably, the catalyst is an organotin compound(for example, dibutyltin dilaurate (DBTDL) or a tertiary amine (forexample, diazobicyclo[2.2.2]octane (DABCO)), or a combination thereof.More preferably, the catalyst is DBTDL.

When fluorochemical alcohols represented by the formulaC₄F₉SO₂NCH₃(CH₂)_(m)OH, wherein m=2 to 4, are reacted with MDI, theprocess described in U.S. patent application Ser. No. 10/751142,entitled “Process For Preparing Fluorochemical Monoisocyanates,” filedon Dec. 31, 2003, can be used.

Fluoroacrylates useful in the compositions of the invention can berepresented by the following general formula:C₄F₉—X—OC(O)NH-A-HNC(O)O—(C_(p)H_(2p))(O)COC(R′)═CH₂

wherein:

-   -   R=H or an alkyl group of 1 to 4 carbon atoms,    -   m=2 to 8,    -   R_(f)=C_(n)F_(2n+1),    -   n=1 to 5,    -   y=0 to 6,    -   q=1 to 8,    -   A=an unbranched symmetric alkylene group, arylene group, or        aralkylene group,    -   p=2 to 30, and    -   R′=H, CH₃, or F.

Preferably, q is 2.

Preferably, X is

and m is 2 to 4.

Preferably, A is selected from the group consisting of C₆H₁₂,

and

more preferably, A is

Preferably, p is 2 to 12; more preferably, p is selected from the groupconsisting of 2, 4, 6, 10, and 12; most preferably, p is 2.

Preferably, R′ is H.

The fluoroacrylates described above can be reacted with co-reactantscomprising two or more acrylate groups to form copolymers that areuseful in the compositions of the invention. Preferably, the co-reactantis a tri(meth)acrylate or a di(meth)acrylate (that is, a compoundcomprising three or two acrylate groups). More preferably, it is adi(meth)acrylate (that is, a compound comprising two acrylate groups).

Useful tri(meth)acrylates include, for example, trimethylolpropanetri(meth)acrylate, propoxylated trimethylolpropane triacrylates,ethoxylated trimethylolpropane triacrylates, tris (2-hydroxyethyl)isocyanurate triacrylate, and pentaerythritol triacrylate. Usefuldi(meth)acrylates include, for example, ethylene glycoldi(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycoldi(meth)acrylate, tetraethylene glycol di(meth)acrylate, 1,4-butanedioldi(meth)acrylate, 1,6-hexanediol di(meth)acrylate, alkoxylated1,6-hexanediol diacrylates, tripropylene glycol diacrylate, dipropyleneglycol diacrylate, cyclohexane dimethanol di(meth)acrylate, alkoxylatedcyclohexane dimethanol diacrylates, ethoxylated bisphenol Adi(meth)acrylates, neopentyl glycol diacrylate, polyethylene glycoldi(meth)acrylates, polypropylene glycol di(meth)acrylates, urethanedi(meth)acrylates andCH₂═CHCO₂CH₂CH₂OC(O)NHC₆H₄CH₂C₆H₄NHCOOCH₂CH₂OC(O)CH═CH₂(HMH). Preferreddi(meth)acrylates include, for example polyethylene glycoldi(meth)acrylates, polypropylene glycol di(meth)acrylates,1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, andHMH.

Fluorinated di(meth)acrylates such as, for exampleC₄F₉SO₂N(CH₂CH₂OC(O)CH═CH₂)₂ andCH₂═CHCO₂CH₂CF₂(OCF₂CF₂)_(n)(OCF₂)_(m)CH₂OC(O)CH═CH₂, are also useful.

Many useful co-reactants are commercially available.

The fluoroacrylate and co-reactant can also be copolymerized with one ormore optional comonomers or functionalized comonomers in order to modifythe properties and performance for different applications.

The peel force of the coatable compositions of the invention can betailored by varying the amount and type of co-reactant used.

Chain transfer agents can be used to promote chain termination and limitgel formation. Useful chain transfer agents include, for example,thiols, secondary alcohols, and polyhalocarbons. Examples ofcommercially available chain transfer agents include tetrabromomethane,isopropanol, 1-hexanethiol, 1-heptanethiol, 1-octanethiol,1-nonanethiol, 1-decanethiol, 1-dodecanethiol, 1-octadecyl mercaptan,1-pentadecanethiol, 1-hexadecyl mercaptan, tert-nonyl mercaptan,tert-hexadecyl mercaptan, tert-tetradecyl mercaptan,2-(butylamino)ethanethiol, 11-mercapto-1-undecanol, n-butyl3-mercaptopropionate, thioglycolic acid, 3-mercaptopropionic acid,4-mercaptobutyric acid, 11-mercaptoundecanoic acid,2-mercaptoethanesulfonic acid, 6-mercapto-1-hexanol, mercaptoacetic acidn-octyl ester, 3-mercaptopropyltrimethoxysilane,3-mercaptoproyltriethoxysilane, 2-mercaptoethyltriethoy silane,3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropionic acidoctadecyl ester, 2-ethylehexyl 3-mercaptopropionate,1H,1H,2H,2H-perfluorohexanethiol, 1H,1H,2H,2H-perfluorododecyl-1-thiol.

Comonomers such as, for example, alkyl acrylates can improve durabilityand film-forming properties. Representative examples of usefulcomonomers include methyl(meth)acrylate, butyl acrylate,isobutyl(meth)acrylate, hexyl acrylate, dodecyl acrylate, and octadecylacrylate.

Other comonomers can modify properties such as, for example, adhesion,hydrophilicity, reactivity, or glass transition temperature. Groups thatare useful in comonomers include, for example, hydroxy, carboxy,quaternary ammonium, acetate, pyrrolidine, polyethylene glycol, sulfonicacid, trialkoxysilane, and silicone. Useful comonomers include, forexample, hydroxy ethyl acrylate, hydroxy butyl acrylate, hydroxy hexylacrylate, hydroxy decyl acrylate, hydroxy dodecyl acrylate, acrylicacid, methacrylic acid, N-vinyl 2-pyrrolidinone, and hydroxypropylacrylic acid, 2-methacryloxypropyltrimethoxysilane,3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane,3-methacryloxypropyltrichlorosilane, glycidyl methacrylate, glycidylacrylate, N-methylol methacrylamide, and N-methylol acrylamide.

The copolymers useful in the coatable compositions of the invention canbe prepared, for example, by combining the fluoroacrylate andco-reactant in a reaction solvent. Typically the weight ratio ofco-reactant to fluoroacrylate is about 35:65 or less. Preferably, theweight ratio is about 20:80 or less (more preferably, 15:85 or less)when there is no chain transfer agent.

Comonomers can typically be present in amounts up to about 30 weightpercent (preferably, about 5 to about 10 weight percent), based upon thetotal weight of monomers.

Useful reaction solvents include esters (for example, ethyl acetate),ketones (for example, methyl ethyl ketone), ethers (for example,methyl-tert-butyl ether), amides (for example, dimethyl formamide), andalcohols.

Preferably, the reaction mixture is agitated. The reaction can generallybe carried out at a temperature between about room temperature and about120° C. (preferably, between about 50° C. and about 70° C).

The reaction is carried out using an initiator. Useful initiatorsinclude, for example, substituted azonitrile compounds, peroxides,peracids, and peresters. Specific examples of useful initiators include2,2-azo-bis-(isobutyronitrile), dimethyl 2,2′-azo-bis-isobutyrate,azo-bis-(diphenylmethane), 4-4′-azo-bis(4-cyanopentanoic) acid,1,1′azo-bis-(cyclohexane carbonitrile), 2,2′-azo-bis-(2-methylbutyronitrile), 2,2′-azo-bis-(2,4-dimethyl valeronitrile),azo-bis-dimethyl valeronitrile, 4,4′-azo-bis-(4-cyanovaleric acid),benzoyl peroxide, cumyl peroxide, tert-butyl peroxide, cyclohexanoneperoxide, glutaric acid peroxide, lauroyl peroxide, methyl ethyl ketoneperoxide, hydrogen peroxide, hydroperoxides such as tert butylhydroperoxide and cumene hydroperoxide, peracetic acid, perbenzoic acid,diisopropyl percarbonate, and the like.

Typically, the polymerization of multifunctional acrylates results ingelling, and therefore the resulting compositions are not coatable (see,for example, Principles of Polymerization, 2^(nd) ed., Wiley & Sons, p.114 (1981)). Surprisingly, however, when fluoroacrylates andmultifunctional acrylates are polymerized using the method of theinvention, gelling does not occur.

The coatable compositions of the invention can be used to impart releaseproperties or water-and oil-repellency to a wide variety of substrates.The coatable compositions are preferably diluted or dispersed in aliquid (for example, water and/or an organic solvent) before coating asubstrate. Preferably, the coating compositions contain from about 5 toabout 15 percent solids (more preferably, about 2 to about 10 percent),based upon the weight of the coating composition.

The coatable compositions can be applied to fibrous substrates (forexample, woven, knit, and non-woven fabrics, textiles, carpets, leather,or paper) to impart water- and oil-repellency.

The coatable compositions can be applied to a substrate (or articlescomprising a substrate) by standard methods such as, for example,spraying, padding, dipping, roll coating, brushing, or exhaustion. Thecomposition can then be dried to remove any remaining water or solvent.Preferably, the coated composition is heated to a temperature betweenabout 100° C. and about 175° C.

The coatable compositions are useful as release coatings, and can beapplied to surfaces requiring release properties from adhesives.Surprisingly, dried coatable compositions of the invention showsignificant solvent resistance. The coatable compositions can thereforebe used as release coatings for solvent cast adhesives. Substratessuitable for release coatings include, for example, paper, metal sheets,foils, non-woven fabrics, polyolefin coated paper, and films ofthermoplastic resins such as polyesters, polyamides, polyolefins,polycarbonates, and polyvinyl chloride.

Release coating compositions can be applied to suitable substrates byconventional coating techniques such as, for example, wire-wound rod,direct gravure, offset gravure, reverse roll, air-knife, and trailingblade coating. The resulting release coating compositions can provideeffective release for a wide variety of pressure sensitive adhesivessuch as, for example, natural rubber based adhesives, silicone basedadhesives, acrylic adhesives, and other synthetic film-formingelastomeric adhesives.

EXAMPLES

Objects and advantages of this invention are further illustrated by thefollowing examples, but the particular materials and amounts thereofrecited in these examples, as well as other conditions and details,should not be construed to unduly limit this invention. Designator Name,Formula and/or Structure Availability PEGDA-700 Polyethylene glycoldiacrylate Sigma Aldrich, CH₂═CHCO₂(C₂H₄O)_(n)C(O)CH═CH₂ Mn Ca. 700Milwaukee, WI PEGDA-1100 Polyethylene glycol (1000) ABCR GmbH & CO.diacrylate KG, Karlsruhe CH₂═CHCO₂(C₂H₄O)_(n)C(O)CH═CH₂ GERMANY Mn ca.1100 DEGDA Diethylene glycol diacrylate Sigma AldrichCH₂═CHCO₂(C₂H₄O)₂C(O)CH═CH₂ SR-344 Polyethylene glycol (400) Sartomerdiacrylate (Mw-508) Company CH₂═CHCO₂(C₂H₄O)_(n)C(O)CH═CH₂ Exton, PASR-610 Polyethylene glycol (600) Sartomer diacrylate (Mw ˜742) CompanyCH₂═CHCO₂(C₂H₄O)_(n)C(O)CH═CH₂ Exton, PA SR-644 Polypropylene glycol(400) Sartomer dimethacrylate Company CH₂═CMeCO₂(C₂H₄O)_(n)C(O)CMe═CH₂Exton, PA SR-230 Diethylene glycol diacrylate Sartomer (DEGDA)CH₂═CHCO₂C₂H₄OC₂H₄OCO₂CH═CH₂ Company Exton, PA SR-213 1,4-Butanedioldiacrylate Sartomer (BDDA) CH₂═CHCO₂(CH₂)₄OC(O)CH═CH₂ Company Exton, PAHDDA 1,6-Hexanediol diacrylate Sigma Aldrich CH₂═CHCO₂(CH₂)₆OC(O)CH═CH₂ODA Octadecyl acrylate Sigma Aldrich CH₂═CHCO₂(CH₂)₁₇CH₃ BA n-Butylacrylate Sigma Aldrich CH₂═CHCO₂(CH₂)₃CH₃ VC12 Vinylidene chloride SigmaAldrich CH₂═CCl₂ DMAEMA 2-(Dimethylamino)ethyl Sigma Aldrichmethacrylate CH₂═CMeCO₂CH₂CH₂NMe₂ IEM 2-Isocyanatoethyl methacrylateSigma Aldrich CH₂═CMe CO₂CH₂CH₂NCO BO 2-Butanone oxime Sigma AldrichHO—N═CMeCH₂CH₃ A-174 3-Methacryloxypropyltrimethoxysilane Sigma Aldrich,CH₂═C(CH₃)CO₂C₃H₆Si(OMe)₃ NMA N-(Hydroxymethyl)methacrylamide SigmaAldrich CH₂═CMeCONHCH₂OH DBTDL Dibutyltin dilaurate Sigma Aldrich DDSDodecylthiol; Sigma Aldrich CH₃(CH₂)₁₁SH TDDM t-Dodecyl mercaptan SigmaAldrich A-189 3-Mercaptopropyltrimethoxysilane Sigma Aldrich HS(CH₂)₃Si(OMe)₃ HEA 2-Hydroxyethyl acrylate; Sigma AldrichHOCH₂CH₂OC(O)CH═CH₂ MDI 4,4′-methylenebis(phenyl Sigma-Aldrichisocyanate);

EtOAC Ethyl acetate Sigma-Aldrich CH₃CO₂CH₂CH₃ DMF N,N-DimethylformamideSigma-Aldrich HC(O)NMe₂ IPA Isopropanol Sigma-Aldrich (CH₃)₂CHOH MEKMethyl ethyl ketone Sigma-Aldrich NMP N-methylpyrrolidone Sigma-AldrichTMPTA Trimethylolpropane Triacrylate Sartomer SR-351(CH₂CHCOOCH₂)₃CC₂H₅) Company Exton, PA PETA Pentaerythritoltetraacrylate Sartomer SR-494 Company Exton, PA LTMDA Perfluoropolyetherdiacrylate Solvay Solexis, CH₂═CHCO₂(C₂F₄O)_(n)(CF₂O)_(m)C(O)CH═CH₂ Inc.Italy Mn ca. 2000 VAZO-67 2,2′azobis(2-cyanopentane) DuPont, Wilmington,DETest Method:Dynamic Contact Angle Measurement

A test solution, emulsion, or suspension (typically at about 3% solids)was applied to nylon 66 film (available from DuPont) by dip-coatingstrips of the film. Prior to coating the film was cleaned with methylalcohol. Using a small binder clip to hold one end of the nylon film,the strip was immersed in the treating solution, and then withdrawnslowly and smoothly from the solution. The coated strip was allowed toair dry in a protected location for a minimum of 30 minutes and then wascured for 10 minutes at 150° C.

Advancing and receding contact angles on the coated film were measuredusing a CAHN Dynamic Contact Angle Analyzer, Model DCA 322 (a Wilhelmybalance apparatus equipped with a computer for control and dataprocessing, commercially available from ATI, Madison, Wis.). Water andhexadecane were used as probe liquids. Values for both water andhexadecane are reported.

Preparation of CH₂═CHCO₂CH₂CH₂OC(O)NHC₆H₄CH₂C₆H₄NHCOOCH₂CH₂OC(O)CH═CH₂(HMH or HEA-MDI-HEA)

A solution of 69.0 g 4,4′-methylenebis(phenyl isocyanate) (0.276 mol)and 85.0 g (0.733 mol) 2-hydroxyethyl acrylate in 400 mL anhydrous THFwas treated with 3 drops DBTDL. A mild exotherm ensued and the mixturewas stirred at 50° C. for 3 hours. Infrared spectroscopy indicatedcomplete conversion of the isocyanate. The THF was allowed to evaporateand the residue was slurried in 400 mL water for 2 hours, filtered, andthe white solid was washed well with water and dried to 129.8 g. H-NMRconfirmed the desired structure in high purity.

Preparation of CH₂═CMeCO₂CH₂CH₂NHC(O)O—N═CMeCH₂CH₃ (IEMEKO)

To a 120 ml bottle was added 15.5 g (100 mmole) 2-isocyanatoethylmethacrylate (IEM), 8.7 g 2-butanone oxime (BO, 100 mmole), 56 mL ethylacetate, 2 drops DBTDL and 3 mg phenothiazine under nitrogen. Thesolution was heated to 60° C., and reacted for 24 hours. Infraredspectroscopy analysis indicated the complete conversion of theisocyanate.

Preparation of C₄F₉SO₂N(CH₃)CH₂CH₂OH (MeFBSE)

MeFBSE was prepared by essentially following the procedure described inU.S. Pat. No. 6,664,354 (Savu et al.), Example 2, Part A.

Preparation of C₄F₉SO₂N(CH₃)C₂H₄OC(O)NHC₆H₄CH₂C₆H₄NCO (MeFBSE-MDI)

A one liter, three-necked round bottom flask, fitted with a heater,nitrogen inlet, reflux condenser and thermocouple was charged withMeFBSE (357.0 g; 1.0 mole) MEK (600 mL) and heated to reflux, whiledistilling out 30 mL of MEK. The mixture was then cooled to 30° C. andtreated with MDI (750 g; 3.0 mole). The temperature of the mixture wasthen increased to about 40° C. for 4 hours, filtered and added totoluene (4 l). The resulting off white precipitate was collected byfiltration, and re-crystallized from toluene (white solid; 689.4 g; 57%yield). Structure was confirmed using liquid chromatography/massspectroscopy (LC/MS) and LC/UV analysis.

Preparation of C₄F₉SO₂N(CH₃)C₂H₄OC(O)NHC₆H₄CH₂C₆H₄NHCOOCH₂CH₂OC(O)CH═CH₂(MeFBSE-MDI-HEA or C4MH)

A one liter flask containing 500 ml ethyl acetate was heated to ref luxunder N₂, and 100 mL of ethyl acetate was distilled out. The remainingsolvent was cooled under dry air and treated with 151.9 g MeFBSE-MDI,29.1 g 2-hydroxyethyl acrylate, 2 drops DBTDL, and 7 mg phenothiazine.After 5 hr at 50° C., infrared spectroscopy indicated completeconversion of the isocyanate. The cloudy solution was filtered through40 g diatomaceous earth and rinsed with hot ethyl acetate to give 473.5g clear solution, (29.6% solids, yield as MeFBSE-MDI-HEA, 77%).

Preparation of C₄F₉SO₂N(CH₃)CH₂CH₂OC(O)CH═CH₂ (MeFBSEA)

MeFBSEA was prepared by essentially following the procedure described inU.S. Pat. No. 6,664,354 (Savu et al.) Example 2, Part A & B.

Preparation of C₄F₉SO₂N (CH₂CH₂OC(O)CH═CH₂)₂ (MFBSEEAAE)

MeFBSEEAA was prepared by following the procedure described in U.S. Pat.No. 6,238,798 (Kang et al.).

Preparation of an acrylic ester of a polyether,CH₃(OCH₂CH₂)_(n)OC(O)CH═CH₂ (CW750A)

An acrylate ester of a polyether containing an average of about 16repeating ethoxy units was prepared as described in U.S. Pat. No.5,648,166 (see Example 3).

General Procedure for Examples and Comparative Examples Listed in Tables1-3

For each example and comparative example, a 120 ml bottle was chargedwith 3.0-10.0 g of the fluoroacrylate listed in the table (preparedessentially as described above for MeFBSE-MDI-HEA), 0-25 % diacrylate byweight and optionally a third hydrocarbon (meth)acrylate monomer in thepresence or absence of a chain transfer agent, 15-40 mg VAZO-67, andsufficient ethyl acetate to yield a 15-30% by weight concentration ofmonomers. After purging with nitrogen for 35-60 seconds, the bottle wassealed and the mixture polymerized in a 70° C. oil bath for 17-44 hrs.The obtained polymers were then examined visually to determine if theyhad gelled and recorded in Table 1 and 2 below. The advancing andreceding contact angles for the resulting polymers were determined asdescribed above and the results were reported in Table 3 below.

Detailed Procedures for Selected Examples in Table 1 Example 1Preparation of C4MH/PEGDA-700 (90/10) at 20% Solids

A 1 liter bottle was charged with 246 g C4MH solution (36.6% solid, 90 gsolid, MW=723, 124.5 mmol) in ethyl acetate (EtOAc), 10 g polyethyleneglycol diacrylate with molecular weight ˜700 (PEGDA-700), 244 gadditional EtOAc and 1.0 g VAZO-67. A magnetic stir bar was added. Thesolution was bubbled with nitrogen for two minutes. The sealed bottlewas put in a 70° C. oil bath and polymerized with magnetic stirring for24 hours. The obtained 20% solid polymer solution was a clear solutionwithout gelation at 70° C. Some polymer crystallization occurred whencooled to room temperature. The crystallized polymer was re-dissolved bysimply heating the solution or adding a polar solvent such asN,N-dimethylformamide (DMF) or N-methylpyrrolidone (NMP).Chromatographic analysis of the solution showed Mn˜11,300, Mw˜121,000,and Mw/Mn=1.02. Contact angles were measured and reported Table 3.

Comparative Example 1 (C1) Preparation of C4MH/PEGDA-700 (80/20) at 20%Solids

A 120ml bottle was charged with 21.37 g C4MH solution (37.5 % solid,8.01 g solid, MW=723, 4.15 mmol) in ethyl acetate (EtOAc), 2.03 gpolyethylene glycol diacrylate with molecular weight ˜700 (PEGDA-700),26.8 g additional EtOAc and 0.15 g VAZO-67. A magnetic stir bar wasadded. The solution was bubbled with nitrogen for two minutes. Thesealed bottle was put in a 70° C. oil bath and polymerized with magneticstirring. The polymer solution gelled after 10 hours.

Example 21 Preparation of C4MH/PEGDA-700/NMA (86/10/4) at 20% Solids

A 120 ml bottle was charged with 22.97 g C4MH solution (37% solid, 8.5 gsolid, MW=723, 11.75 mmol) in ethyl acetate (EtOAc), 1.5 g polyethyleneglycol diacrylate with molecular weight ˜700 (PEGDA-700), 2.08 g NMAaqueous solution (˜48% solid, 0.998 g solid), 28.45 g IPA and 0.15 gVAZO-67. A magnetic stir bar was added. The solution was bubbled withnitrogen for two minutes. The sealed bottle was put in a 70° C. oil bathand polymerized with magnetic stirring for 24 hours. A 20% solid clearpolymer solution was obtained without gelation at 70° C. Some polymercrystallization occurred when cooled to room temperature. Thecrystallized polymer was re-dissolved by simply heating the solution oradding a polar solvent such as N,N-dimethylformamide (DMF) orN-methylpyrrolidone (NMP).

Comparative Example 9 (C9) Preparation of MeFBSEA/PEGDA-700 (90/10) at20% Solids

A 120 ml bottle was charged with 4.5 g MeFBSEA (MW=411, 10.9 mmol), 0.50g polyethylene glycol diacrylate with molecular weight ˜700 (PEGDA-700),20 g EtOAc and 20 mg VAZO-67. A magnetic stir bar was added. Thesolution was bubbled with nitrogen for two minutes. The sealed bottlewas put in a 60° C. oil bath and polymerized with magnetic stirring. Thepolymer solution gelled after 10 hours. TABLE 1 Examples 1-33 andComparative Examples C1-C12 Example Formulation Wt ratio Solid % Hours @60˜70° C. Results 1 C4MH/PEGDA-700 90/10 20 44 OK 2 C4MH/PEGDA-700 85/1520 24 OK C1 C4MH/PEGDA-700 80/20 20 24 Gelled 3 C4MH/PEGDA-700 80/20 1524 OK 4 C4MH/PEGDA-700 90/10 25 24 OK C2 C4MH/PEGDA-700 90/10 30 24Gelled 5 C4MH/PEGDA-1100 80/20 20 24 OK 6 C4MH/SR-644 90/10 20 24 OK 7C4MH/SR-644 85/15 20 24 OK 8 C4MH/SR-213 90/10 20 44 OK C3 C4MH/SR-21380/20 20 4 Gelled 9 C4MH/HMH 100/0 20 44 OK 10 C4MH/HMH 95/5 20 44 OK 11C4MH/HMH 90/10 20 44 OK 12 C4MH/HMH 85/15 20 44 OK C4 C4MH/HMH 80/20 2019 Gelled 13 C4MH/HDDA 95/5 20 44 OK 14 C4MH/HDDA 90/10 25 24 OK 15C4MH/HDDA 85/15 25 24 OK 16 C4MH/PEGDA-700/ODA 70/10/20 20 24 OK 17C4MH/PEGDA-700/VCl₂ 80/10/10 20 24 OK 18 C4MH/PEGDA-700/DMAEMA 85/10/520 24 OK 19 C4MH/PEGDA-700/IEMEKO 80/10/10 20 24 OK 20C4MH/PEGDA-700/A-174 86/10/4 20 24 OK 21 C4MH/PEGDA-700/NMA 77/14/9 2024 OK 22 C4MH/CW750A/HMH 85/10/5 20 44 OK 23 C4MH/CW750A/DEGDA 85/10/520 44 OK 24 C4MH/CW750A/BDDA 85/10/5 20 44 OK 25 C4MH/CW750A/HDDA 89/9/220 20 OK C5 C4MH/CW750A/HDDA 84/9/7 20 20 Gelled 26 C4MH/ODA/HDDA63/27/10 15 24 OK 27 C4MH/BA/HMH 90/10/5 20 44 OK 28 C4MH/TMPTA 90/10 2024 OK C6 C4MH/TMPTA 80/20 20 17 Gelled 29 C4MH/PETA 90/10 20 17 OK C7C4MH/PETA 80/20 20 17 Gelled C8 MeFBSEA/TMPTA 90/10 20 17 Gelled C9MeFBSEA/HDDA 90/10 20 22 Gelled C10 MeFBSEA/HDDA 85/15 20 15 Gelled C11MeFBSEA/HMH 90/10 20 22 Gelled C12 MeFBSEA/PEGDA-700 90/10 20 22 Gelled30 C4MH/FBSEEAA 90/10 20 24 OK 31 C4MH/FBSEEAA/SR-610 90/5/5 20 24 OK 32C4MH/LTMDA 90/10 20 24 OK 33 C4MH/LTMDA/SR-610 80/10/10 20 24 OKEffect of Chain Transfer Agent

Detailed Procedures for Selected Examples in Table 2 Example 35Preparation of C4MH/PEGDA-700/DDS (76/20/4) at 30% Solids

A 120 ml bottle was charged with 4.50 g C4MH solid (MW=723, 5.53 mmol),0.50 g PEGDA-700, 0.10 g DDS, 11.67 g EtOAc and 0.049 g VAZO-67. Amagnetic stir bar was added. The solution was bubbled with nitrogen fortwo minutes. The sealed bottle was put in a 70° C. oil bath andpolymerized with magnetic stirring for 24 hours. A clear polymersolution (20% solids) was obtained without gelation at 70° C. Somepolymer crystallization occurred when cooled to room temperature. Thecrystallized polymer was re-dissolved by simply heating the solution oradding a polar solvent such as N,N-dimethylformamide (DMF) orN-methylpyrrolidone (NMP). Chromatographic analysis of the solutionshowed that the conversion was 92% and Mn˜8,960, Mw˜50,200, andMw/Mn=5.6.

Example 41 Preparation of C4MH/PEGDA-700/A-189 (88/10/2) at 25% Solids

A 500 ml bottle was charged with 45.0 g C4MH solid (MW=723, 62.2 mmol),5.0 g PEGDA-700, 0.50 g A-189, 151.5 g EtOAc and 1.25 g VAZO-67 (2.47%).A magnetic stir bar was added. The solution was bubbled with nitrogenfor two minutes. The sealed bottle was put in a 70° C. oil bath andpolymerized with a magnetic stirring for 24 hours. A clear polymersolution (20% solids) was obtained without gelation at 70° C. Somepolymer crystallization occurred when cooled to room temperature. Thecrystallized polymer was re-dissolved by simply heating the solution oradding a polar solvent such as N,N-dimethylformamide (DMF) orN-methylpyrrolidone NMP). Chromatographic analysis of the solutionshowed that the conversion was 95.4% and Mn˜7270, Mw˜56500, andMw/Mn=7.8. TABLE 2 Examples 34-46 and Comparative Example C13 ExampleFormulation Wt ratio Solid % Hours @ 60-70° C. Results 34C4MH/PEGDA-700/DDS 88/10/2 30 24 OK 35 C4MH/PEGDA-700/DDS 76/20/4 20 24OK 36 C4MH/PEGDA-700/DDS 68/30/2 20 44 OK 37 C4MH/PEGDA-700/DDS 65/33/220 24 OK C13 C4MH/PEGDA-700/DDS 60/38/2 20 24 Gelled 38C4MH/PEGDA-700/ODA/DDS 68/10/20/2 20 24 OK 39 C4MH/ODA/HDDA/TDDM53/22/19/6 25 24 OK 40 C4MH/PEGDA-700/A-189 84/15/1 25 24 OK 41C4MH/PEGDA-700/A-189 88/10/2 30 24 OK 42 C4MH/PEGDA-700/A-189/A-17484/9/2/5 20 24 OK 43 C4MH/PEGDA-700/A-189/VCl₂ 84/9/2/5 20 24 OK 44C4MH/SR-644/A-189 79/20/1 20 24 OK 45 C4MH/SR-344/A-189 89/10/1 25 24 OK46 C4MH/SR-610/A-189 89/20/1 25 24 OK

Contact angles for selected materials were measured as described aboveand the results are reported in Table 3 below. TABLE 3 Examples 47-65and Comparative Examples C14-C16 Contact Angle (advancing/ receding)Exam- Hexa- ple Formulation Wt Ratio Water decane 47 C4MH/PEGDA-70080/20 129/104 80/71 48 C4MH/SR-644 90/10 124/101 77/66 49 C4MH/HMH 90/10121/91  80/70 50 C4MH/PEGDA-700/ODA 70/10/20 126/96  80/59 51C4MH/PEGDA-700/VCl₂ 80/10/10 123/107 80/70 52 C4MH/PEGDA-700/DMAEMA85/10/5 128/111 82/70 53 C4MH/PEGDA-700/IEMEKO 80/10/10 125/101 80/68 54C4MH/CW750A/HMH 90/10/5 120/101 82/70 55 C4MH/PEGDA-700/DDS 86/10/4119/108 78/68 56 C4MH/PEGDA-700/A-189 88/10/2 128/112 83/68 57C4MH/PEGDA-700/A-189 89/10/1 113/91  82/64 58 C4MH/PEGDA-700/A-18984/15/1 128/101 81/70 59 C4MH/SR-644/A-189 79/20/1 122/100 79/67 60C4MH/SR-344/A-189 89/10/1 132/111 81/70 61 C4MH/SR-610/A-189 89/20/1126/108 81/70 C14 MeFBSEA/PEGDA-700/A-189 89/10/1 118/46  76/44 62C4MH/FBSEEAA 90/10 130/96  82/71 63 C4MH/FBSEEAA/SR-610 90/5/5 131/10582/71 C15 MeFBSEA/FBSEEAA 90/10 118/82  72/63 64 C4MH/LTMDA 90/10131/110 82/71 65 C4MH/LTMDA/SR-610 80/10/10 116/92  72/68 C16MeFBSEA/LTMDA 90/10 124/80  73/52

Examples 66-73

Polymers of the invention were coated on polyester film and dried at150° C. for 15 minutes. The coated film was cooled to 22° C. at 50%relative humidity in a control room. A 70/30 toluene/isopropanol mixturewas smeared onto the coated films using a cotton swab. After solventevaporated from the film, a 7.6 cm strip of SCOTCH MAGIC TAPE 810(Available from 3M Company) was laminated on the area where the solventmixture was smeared and then peeled off by hand. A smooth low peel forcewas observed on coatings that were resistant to the solvent mixture.These coatings were judged to “pass” the test. If the coating wassoluble in the solvent, a qualitatively high and shocky peel force wasobserved. These coatings were judged to “fail” the test. The results aretabulated in Table 4 below. TABLE 4 Examples 66-73 and ComparativeExamples C17-C19 Example Formulation Result C17 C4MH/ODA(70/30) Fail C18C4MH/HMH(100/0) Fail C19 C4MH/HMH(98/2) Fail 66 C4MH/HMH(95/5) Pass 67C4MH/HMH(90/10) Pass 68 C4MH/PEGDA-700 (90/10) Pass 69C4MH/PEGDA-700/DDS (89/10/1) Pass 70 C4MH/PEGDA-700/DDS (88/10/2) Pass71 C4MH/PEGDA-700/DDS (78/20/2) Pass 71 C4MH/PEGDA-700/A-189 (88/10/2)Pass 73 C4MH/PEGDA-700/A-189/AA {86/10/2/2} Pass

Examples 74-75 Release Coatings

The copolymers of the invention were diluted to 5% solids with toluene.The solution was then coated with a #6 wire around (Mayer) rod onto a1.6 mil primed polyester terephthalate film. The coated film wasattached to a fiberboard frame and dried for 15 minutes at 150° C.

The test method used to evaluate the release coatings was a modificationof the industry standard peel adhesion test used to evaluate pressuresensitive adhesive coated materials. The standard test is described indetail in various publications of the American Society for Testing andMaterials (ASTM), Philadelphia, Pa., and the Pressure Sensitive TapeCouncil (PSTC), Glenview, Ill. The modified standard method is describedin detail below. The reference source of the standard test method isASTM D3330-78 PSTC-1 (11/75).

2.54 cm by 15.24 cm strips of SCOTCH PERFORMANCE MASKING TAPE 233+(available from 3M Company, St. Paul, Minn.) were rolled down onto thecoated polyester film with a 2.04 kg rubber roller. The laminatedsamples were then aged 1 week at 22° C. and 50% relative humidity or 16hours at 65° C. Prior to testing, the heat-aged samples wereequilibrated to 22° C. and 50% relative humidity for 24 hours.

Release testing was conducted by mounting the masking tape/coated filmlaminate to the stage of an Instrumentors, Inc. slip/peel tester (model3M90) with double coated tape. The force required to remove the maskingtape at 180 degrees and 228.6 cm/minute was then measured. Tapere-adhesions were also measured by adhering the freshly peeled maskingtape to a clean glass plate and measuring the peel adhesion in normalfashion using the same Instrumentors slip/peel tester indicated above,again peeling at 228.6 cm/min and at a 180 degree peel angle. Theresults of these peel tests are shown in Table 5.

The backside of a strip of SCOTCH PERFORMANCE MASKING TAPE 233+ servedas a control sample. TABLE 5 Examples 74-75 and Comparative Example C207 Days @ 22° C. 16 hrs @ 65° C. Peel Force Readhesion Peel ForceReadhesion from Release Peel Force from Release Peel Force Coating fromGlass Coating from Glass Example Copolymer Coating (g/cm) (g/cm) (g/cm)(g/cm) 74 C4MH/PEGDA-700/DDS 131 539 161 499 (88/10/2) 75C4MH/PEGDA-700/DDS 206 513 229 468 (78/20/2) C20 SCOTCH PERFORMANCE 198518 397 452 MASKING TAPE 233+

Examples 76-77 Release Coatings

The copolymers of the invention were coated and tested according to themethods described above with the exception that SCOTCH MAGIC TAPE 810(Available from 3M Company) was used in place of SCOTCH PERFORMANCEMASKING TAPE 233+. The backside of a strip of SCOTCH MAGIC TAPE 810served as a control sample. The results are shown in Table 6 below.TABLE 6 Examples 76-77 and Comparative Example C21 7 Days @ 22° C. 16hrs @ 65° C. Peel Force Readhesion Peel Force Readhesion from ReleasePeel Force from Release Peel Force Coating from Glass Coating from GlassExample Copolymer (g/cm) (g/cm) (g/cm) (g/cm) 76 C4MH/PEGDA-700/DDS 77297 101 244 (88/10/2) 77 C4MH/PEGDA-700/DDS 91 294 88 252 (78/20/2) C21SCOTCH MAGIC TAPE 79 265 150 182 810

Examples 78-85 Release Coatings

Release coatings of the invention were prepared and tested according tothe methods described above using a silicone polyurea pressure sensitiveadhesive that was prepared and coated as described in U.S. Pat. No.6,569,521 (see Example 31). The peel force from the release coating andsubsequent readhesion peel force from glass were measured. The resultsare shown in Table 7 below. TABLE 7 Examples 78-85 7 Days @ 22° C. 16hrs @ 65° C. Peel Force Readhesion Peel Force Readhesion from ReleasePeel Force from Release Peel Force Coating from Glass Coating from GlassExample Copolymer (g/cm) (g/cm) (g/cm) (g/cm) 78 C4MH/PEGDA-700/A-189 5565 10 586 (88/10/2) 79 C4MH/PEGDA-700/A- 6 808 13 621 189/AA(86/10/2/2) 80 C4MH/PEGDA-700/A-174 16 677 15 661 (86.5/9.6/3.9) 81C4MH/CW750A/HMH 12 651 12 585 (90/10/5) 82 C4MH/CW750A/BDDA 260 518 190574 (90/10/5) 83 C4MH/HMH 91 684 39 739 (90/10) 84 C4MH/DEGDA 108 761 47496 (90/10) 85 C4MH/BDDA 260 518 190 574 (90/10)

The referenced descriptions contained in the patents, patent documents,and publications cited herein are incorporated by reference in theirentirety as if each were individually incorporated.

Various modifications and alteration to this invention will becomeapparent to those skilled in the art without departing from the scopeand spirit of this invention. It should be understood that thisinvention is not intended to be unduly limited by the illustrativeembodiments and examples set forth herein and that such examples andembodiments are presented by way of example only with the scope of theinvention intended to be limited only by the claims set forth herein asfollows.

1. A composition comprising a copolymer comprising repeating unitsderived from at least one at least one co-reactant comprising two ormore acrylate groups and repeating units derived from a fluoroacrylatecomprising the reaction product of: (a) at least one fluorochemicalalcohol represented by the formula:C₄F₉—X—OH wherein:

R=hydrogen or an alkyl group of 1 to 4 carbon atoms, m=2 to 8,R_(f)=C_(n)F_(2n+1), n=1 to 5, y=0 to 6, and q=1 to 8; (b) at least oneunbranched symmetric diisocyanate; and (c) at least onehydroxy-terminated alkyl (meth)acrylate or 2-fluoroacrylate monomerhaving 2 to about 30 carbon atoms in its alkylene portion; wherein thecomposition is coatable.
 2. The composition of claim 1 wherein theweight ratio of co-reactant to fluoroacrylate is about 35:65 or less. 3.The composition of claim 2 wherein the weight ratio of co-reactant tofluoroacrylate is about 20:80 or less.
 4. The composition of claim 1wherein the co-reactant is a tri(meth)acrylate or a di(meth)acrylate. 5.The composition of claim 4 wherein the co-reactant is adi(meth)acrylate.
 6. The composition of claim 5 wherein the co-reactantis a fluorinated di(meth)acrylate.
 7. The composition of claim 1 whereinthe unbranched symmetric diisocyanate is an aromatic diisocyanate. 8.The composition of claim 1 wherein the copolymer further comprises atleast one chain transfer agent.
 9. The composition of claim 8 whereinthe chain transfer agent is selected from the group consisting ofthiols, secondary alcohols, and polyhalocarbons.
 10. The composition ofclaim 1 wherein the copolymer further comprises repeating units derivedfrom at least one comonomer.
 11. The composition of claim 1 furthercomprising a solvent.
 12. An article comprising a substrate having oneor more surfaces coated with the composition of claim
 1. 13. The articleof claim 12 wherein the substrate comprises a material selected from thegroup consisting of polyethylene terephthalate, polyolefins, andpolyolefin coated paper.
 14. The article of claim 12 wherein thesubstrate is a fibrous substrate.
 15. The article of claim 12 whereinthe article is a release liner.
 16. A composition comprising a copolymercomprising the reaction product of (a) a fluoroacrylate represented bythe following general formula:C₄F₉—X—OC(O)NH-A-HNC(O)O—(C_(p)H_(2p))(O)COC(R′)═CH₂ wherein:

R=H or an alkyl group of 1 to 4 carbon atoms, m=2 to 8,R_(f)=C_(n)F_(2n+1), n=1 to 5, y=0 to 6, q=1 to 8, A=an unbranchedsymmetric alkylene group, arylene group, or aralkylene group, p=2 to 30,and R′=H, CH₃, or F; and (b) at least one co-reactant comprising two ormore acrylate groups; wherein the composition is coatable.
 17. Thecomposition of claim 16 wherein the weight ratio of co-reactant tofluoroacrylate is about 35:65 or less.
 18. The composition of claim 17wherein the weight ratio of co-reactant to fluoroacrylate is about 20:80or less.
 19. The composition of claim 16 wherein the co-reactant is atri(meth)acrylate or a di(meth)acrylate.
 20. The composition of claim 19wherein the co-reactant is a di(meth)acrylate.
 21. The composition ofclaim 20 wherein the co-reactant is a fluorinated di(meth)acrylate. 22.The composition of claim 16 wherein the copolymer comprises the reactionproduct of (a), (b), and at least one chain transfer agent.
 23. Thecomposition of claim 22 wherein the chain transfer agent is selectedfrom the group consisting of thiols, secondary alcohols, andpolyhalocarbons.
 24. The composition of claim 16 wherein the copolymercomprises the reaction product of (a), (b), and at least one comonomer.25. The composition of claim 16 further comprising water or an organicsolvent.
 26. The composition of claim 25 wherein the composition is arelease coating composition.
 27. An article comprising a substratehaving one or more surfaces coated with the composition of claim
 16. 28.The article of claim 27 wherein the substrate comprises a materialselected from the group consisting of polyethylene terephthalate,polyolefins, and polyolefin coated paper.
 29. The article of claim 27wherein the substrate is a fibrous substrate.
 30. The article of claim27 wherein the substrate is a non-woven substrate.
 31. An articlecomprising a substrate having one or more surfaces coated with thecomposition of claim
 26. 32. The article of claim 31 wherein the articleis a release liner.
 33. A method of making a coatable compositioncomprising reacting a fluoroacrylate with at least one co-reactantcomprising two or more acrylate groups, and optionally at least onechain transfer agent, in a reaction solvent to form a copolymer; whereinthe fluoroacrylate, co-reactant, and chain transfer agent are present inan amount up to about 35 weight percent, the weight percent being basedupon the total weight of the monomers and the solvent; and wherein thefluoroacrylate is represented by the following general formula:C₄F₉—X—OC(O)NH-A-HNC(O)O—(C_(p)H_(2p))(O)COC(R′)═CH₂ wherein:

R=H or an alkyl group of 1 to 4 carbon atoms, m=2 to 8,R_(f)=C_(n)F_(2n+1), n=1 to 5, y=0 to 6, q=1 to 8, A=an unbranchedsymmetric alkylene group, arylene group, or aralkylene group, p=2 to 30,and R′=H, CH₃, or F.
 34. The method of claim 33 wherein the co-reactantis present in the copolymer in an amount between about 5 and 5 about 25weight percent.
 35. The method of claim 33 wherein the weight ratio ofco-reactant to fluoroacrylate is about 20:80 or less.